1-alkoxy(-alk enyloxy,-phenoxy)-1-thiono-3-chloro(3-alkyl) phospholines compositions and their use

ABSTRACT

Compositions comprising 1-alkoxy(-alkenyloxy,-phenoxy)-1-thiono3-chloro(3-alkyl) phospholines, i.e., 1-(alkoxy, alkenyloxy, chloroalkoxy, alkylphenoxy, alkylmercaptophenoxy and chlorosubstituted phenoxy)-3-(chloro and alkyl)- Delta 3 and Delta 2phospholines, and their use in combating nematodes, arthropods, especially acarids and insects, and fungi.

0 a Fluted States atem n91 [111 schliebset a1. 5] Apr. 10, 1973 [5 1l-ALKOXY(-ALK ENYLOXY,- [511 Km. c1. mi. 9/36PHENOXY)-l-THIONO-3-C1H4ORO6- [58] Field of Search ..424/209; 260/936ALKYL) PHOSPHOLHIES COMPOSITIONS AND THEN USE References filed [75]Inventors: Reinhard Schliebs, Koeln-Flittard; UNITED STATES PATENTSHanshelmut Schflor, Wuppertal; Bernhard Homeyer, Opladen, of 2,761,8069/1956 Boyer ..260/964 Germany 3,285,999 11/1966 Buchner ..424/209 [73]Assignee: Farbenfabriken Bayer Aktien- Primary Examiner-Albert T. Meyersgeseuschafi, Levelkusen, Germany Assistant ExaminerNorman A. Drezin 22]Filed: Aug 20 1971 Attorney-Ralph D. Dinklage 61 a1.

[21] Appl. No.: 173,677 57 ABSTRACT Related U.S. Application DataCompositions comprising l-alkoxy(-a1kenyloxy,- 62 l Iphen0xy)-1-thiono-3-chloro(3-alkyl) phospholines, 1 Ser No June 1969 PatNo i.e., l-(a1koxy, alkenyloxy, chloroalkoxy, alkylphenoxy,alkylmercaptophenoxy and chloro-substituted [30] Foreign ApplicationPriority Data P y)' and ynand phospholines, and their use in combatingnematodes, June 14, 1968 Germany ..P 17 68 662.3 arthropods especiallyacarids and insects and fungi [52] U.S. Cl. ..424/209 12 Claims, NoDrawings l-ALKOXY(-ALK ENYLOXY,-PHENOX Y)- 1- THIONO- 3-CHLORO(3-ALKYL)PHOSPHOLINES COMPOSITIONS AND THEIR USE This application is a divisionof US. application Ser. No. 830,122, filed June 3, 1969, now US. Pat.No. 3,644,598.

The present invention relates to and has for its objects the provisionof compositions of new l-alkoxy alkenyloxy, -phenoxy 1 -thiono-3-chloro(3-alkyl)phospholines, i.e., l-(alkoxy, alkenyloxy, chloroalkoxy,alkylphenoxy, alkylmercapto-phenoxy and chloro-substitutedphenoxy)-3(chloro and alkyl)-A and A -phospholines, which possessnematocidal, arthropodicidal, especially insecticidal and acaricidal,and fungicidal properties, mixtures of such compounds with solid andliquid dispersible carrier vehicles, and methods for producing suchcompounds and for using such compounds in a new way especially forcombating pests, e. g. nematodes, arthropods, and fungi, with other andfurther objects becoming apparent from a study of the withinspecification and accompanying examples.

Phosphoric or thiophosphoric acid esters with nematocidal activity havebeen known from the literature for some time. Thus, for example, in US.Pat. No. 2 ,76 l ,806, 0,0-diethyl-O-( 2,4-dichloro-phenylthionophosphoric acid ester (A) is described as having a goodeffectiveness in this respect. Furthermore,'0,0-diethyl-O-(4-methylmercapto-phenyl)-thionophosphorric acid ester (B) and0,0-diethyl-O-pyrazin- 2-yl-thionophosphoric acid ester (C) known fromGerman Auslegeschriften 1,101,406 and 1,156,274 are known to bedistinguished by nematocidal effectiveness.

On the other hand, most pesticidally effective phosphoric orthiophosphoric acid esters possess, as is known, a not inconsiderabletoxicity towards warmblooded animals'Thus, for example the median lethaldose of the above-mentioned, 0,0-diethyl-O-(2,4-dichloro-phenyl)-thionophosphoric acid ester (A) in the rat per os is270 mg/kg animal [see G. Schrader Die Entwicklung neuer insektiziderPhosphorsaureester," Verlag Chemie, Weinheim/Bergstrasse, 3rd edition(1963), page 210]. 1

It has now been found, in accordance with the present invention, thatthe particular new 1-alkoxy(-alkenyloxy,-phenoxy 1 -thiono-3 -chloro(3-alkyl )-A and Al-phospholines of the formula dihalogenor l-thiono- 1-halogen-3-alkyl-phospholine of the formula l CCH1 s G=CH s u \n \u PXor P-X 0114142 orb-0 in which R is the same as defined above and X is ahalogen atom such as chloro, bromo, fluoro or iodo, especially chloro,with an alcohol or phenol of the formula HOR (m) in which R is the sameas defined above, preferably in the presence of an acid-binding agent.

Surprisingly, the active compounds according to the present invention,compared to analogous active compounds of the same type of activityhitherto known form the literature, are distinguished by a substantiallybetter effectiveness, in particular outstanding nematocidal propertiesand, in addition, noteworthy insecticidal, acaricidal andsoil-fungicidal activity, with considerably lower toxicity towarm-blooded animals. Therefore, the instant compounds represent avaluable contribution to the art.

The course of the production reaction can be represented by thefollowing formula scheme l R T I' aty P-O-R' CCH2 S CHCH2 1 /PX+HOR'(DH-43H: R

O-R (II) (III) Hz-CH2 4 (I') in which R, R and X are the same as definedabove. 1 Advantageously, in accordance with the present invention, inthe various formulae herein:

R represents chloro, or

straight and branched chain lower alkyl hydrocarbon of one to fourcarbon atoms such as methyl ethyl, nand iso-propyl, n-, iso-, sec.- andtert.-butyl, and the like, especially C or C alkyl, and more especiallymethyl; and

R represents straight and branched chain alkyl hydrocarbon of one to sixcarbon atoms such as methyl to tertbutyl inclusive as defined above,amyl, isoamyl, nhexyl, isohexyl, pinacolyl (i.e., [CH C-[ CH ]CH), andthe like, especially C, or C or C alkyl, and more especially methyl; or

straight and branched chain alkenyl hydrocarbon of two to four carbonatoms such as vinyl, 04-, ,8- and 'y-allyl, but-1,2 and 3-enyl, and thelike, especially C,, alkenyl, more especially C alkenyl, and preferablyu-allyl; or

chloro-alkyl having one to four carbonatoms such as chloromethyl totert.-butyl inclusive as defined above, and the like, especiallychloro-C or C,

alkyl, and more especially 2chloro-ethyl; or alkylphenyl having one tofour carbon atoms in the alkyl moiety such as 2-, 3- and 4-methy1 totert.-

butyl inclusive as defined above, and the like,

phenyl, especially 4- C alkylphenyl; or alkylmercaptophenyl having oneto four carbon atoms in the alkylmercapto to moiety such as 2-, 3-

and 4- methyl to tert.-butyl inclusive as defined above,-mercapto-phenyl, and the like, especially 2-, 3- and 4- C, or C,alkylmercaptophenyl,

preferably methylmercaptophenyl, and particularly4-methylmercaptophenyl; or chloro-substituted phenyl such as 2-, 3- and4-mono, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5- di, and 2,3,4-, 3,4,5-,2,3,6-, 2,4,5- and 2,4,6- tri, and the like, especially tri,-chloro-substituted phenyl, and more especially 2,4,5-tri-chlorophenyl,i.e. mono to tri-chlorophenyl.

In particular, R is chloro; or C, or C, alkyl; R is C alkyl; or Calkylphenyl; or C alkylmercaptophenyl.

It will be realized that the compounds of the present inventioncontemplate both the A and A isomers, i.e., in which the nuclear doublebond is in the 3,4-position and 2,3-position, respectively.

Examples of alcohols suitable for the production process are: methyl,ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, n-amyl,isoamyl, tert.-amy1, 1,2,2- trimethyl propyl, pinacolyl, allyl,2-chloroethyl, and 2,2,2-trichloro-ethyl alcohol; and the like.

Phenols suitable for the instant reaction are for example: 2-, 3- and4-chloro-, 2,4- and 2,5-dichloro-, 2,4,5- and 2,4,6-trichloro-, 2, 3-and -4-methyl-, 2-, 3 and 4-ethyl-, 4-tert.-butyl-, 3-tert.-butyl-; 2-,3- and 4- methyl-; -mercapto-phenol; and the like.

- Examples of l-thiono-1,3-halogenor -l-halogen-3- alkyl-phospholinesaccording to formula (11) above to be reacted according to the presentinvention are: 1- thionol ,3-dichloro-, 1-thiono-l-bromo-3-chloro-, 1-thionol -chloro-3-methylor 1-thiono-l-chloro-3- ethyl-A and A-phospholines; and the like.

Some of the 1-thiono-l,3-halogenor -l-halogen-3- alkyl-phospholines offormula (11) above required as starting materials are described in theliterature and can be prepared, even on an industrial scale, accordingto various known methods.

Either the appropriate oxo compounds are reacted according to the methodof MJ. KABACHNIK (Dokl.Akad.Nauk.SSSR, [Reports of the Academy ofSciences of the USSR] 1 (1956), page 217) according to the followingequation with phosphorus pentasulfide 0030 in which R and X are, in eachcase, the same as defined above.

The oxo-phospholines required for the first-mentioned process arereadily accessible according to the particulars given by G.M. BOGOLYUBOVet.al (Z.0bs. chim. Journal of General Chemistry [USSR], Vol 33 [1963],pages 783 and 2419) and in German Patent (DAS)1,199,264.

As can be seen from the above formulae (1) and (1), in theesterification reaction there may occur a migration of the double bondof the thionophospholine ring from the 3,4-position (i.e.,A into the2,3-position (i.e.,A'-') and vice versa. Mixtures of two isomers aretherefore obtained in the reaction. Such shifts of double bonds inphospholines are known from the literature (see for example H.WEITKAMPand A.KORTE, Z. analyt. Chem. Vol. 204, (1964), pages 245 to 263 and K.HASSERODT et.al. Tetrahedron, Vol. 19, (1963), page 1563." According toWEITKAMP and KORTE (loc.cit.), the exact position of the double bond canbe ascertained by nuclear resonance and ultraviolet spectroscopy.Moreover, it is readily possible to separate the two isomers by suitableseparation methods (for example separating columns, preparative gaschromatography or fractional distillation over particularly efficientcolumns). The course of such a separation and the purity of the productsobtained can be followed, or determined, by thin-layer chromatography.Even in the case of the above-mentioned preparation of the startingproducts by sulfurization of the appropriate oxo compounds, a shift ofthe double bond in the manner stated can also occur.

Since, however, both isomers (i.e.,A and A are practically equaleffective pesticidally, as has been found in accordance with the presentinvention, separation of the mixture is not necessary for their use aspesticides. The strongly biocidal, in particular nematocidal,effectiveness of the particular new compounds of formulae (1) and (1')according to the present invention could not in any way be foreseensince the instant compounds prove almost non-toxic to warm-bloodedanimals and also neither an insecticidal activity nor any particularbiological effect was known for compounds of analogous constitution. Thenew compounds according to the present invention therefore represent agenuine enrichment of the art, as aforesaid.

The production reaction according to the present invention is preferablycarried out in the presence of a solvent (the term solvent includingmere diluents). As such, an excess of the reactant alcohol may be usedif it is liquid under the conditions of the reaction. Otherwise, or inaddition, inert organic solvents are suitable, such as ketones (forexample acetone, methylethyl, methylisopropyl or methylisobutyl ketone);ehters (for example diethyl ether, di-n-butyl ether, dioxan ortetrahydrofuran); as well as (possibly chlorinated) aliphatic oraromatic hydrocarbons (for example methylene chloride, di-, triandtetra-chloroethane, chloroform, carbon tetrachloride, benzene,chlorobenzene, toluene or xylene); and the like.

As already mentioned above, preparation of the new compounds accordingto the present invention is preferably carried out in the presence of anacid-binding agent. Suitable for this purpose are, in particular, alkalimetal alcoholates, hydroxides and carbonates, such as potassium orsodium methylate, ethylate,

hydroxide or carbonate; also, aliphatic, aromatic and heterocylic bases,for example triethylamine, diethylaniline, benzyldimethylamine andpyridine; and the like. I The 'esterification reaction temperature canbe varied within a fairly wide range. In general, the reaction iscarried out at substantially between about to 80 C, preferably atbetween about 10 to 50 C.

To prepare the instant new compounds, 2 to 10 mols I of the alcohol tobe esterified are preferably used per mol of l-thiono-l,3-dihalogenor-l-halogen-3-alkyl phospholine. In the case of reactions using phenols,

' however, stoichiometric amounts or a slight excess only lization ofthe residue. When the products are obtained in the form of viscous,non-crystallizing or non-distillable oils, they can, by so-called slightdistillation," that is by brief heating in a vacuum to slightly tomoderately elevated temperatures, be freed from the last solventresidues and other volatile components and in this way be purfied.

As noted above, the active compounds according to the present inventionare distinguished by an outstanding, rapidly-commencing nematocidaleffectiveness, with only slight toxicity to warm-blooded animals andonly slight phytotoxicity, and possess, in addition, a markedly goodinsecticidal, acaricidal and soil-fungicidal effect. I

By reason of these properties, the instant active compounds may be usedadvantageously in plant protection for the control of nematodes,especially those of phytopathogenic nature. In view of the simulatneousinsecticidal, acaricidal and soil-fungicidal activity of the instantcompounds, any sucking or eating insects, Diptera or mites, orsoil-inhabiting phytopathogenic fungi, which may be present aredestroyed at the same time. As a result of this broad spectrum ofactivity of the instant compounds, the necessity for separate control ofthe various types of pests (which often occur together) does not arise,a fact which represents a further considerable technological advance.

To the phytopathogenic nematodes contemplated herein there belong, inthe main, leaf nematodes (Aphelenchoides), such as chrysanthemum foliarnematodes (A. ritzenmabosi), strawberry nematodes (A. fragariae) andrice nematodes (A. oryzae); stem nemodes (Ditylenchus), for example thestem nematode (D. dipsaci); root gall nematodes (Meloidogyne), such asM. arenaria and M. incognita; cyst-forming nematodes (Heterodera), suchas golden nematode of potato (H. rostochiensis), and sugar beet nematode(H. schachu'i); and free-living root nematodes, for example those of thegenera Pratylenchus, Pratylenchus, Rotylenchus, Xiphinema andRadopholus; and the like.

To the sucking insects contemplated herein there belong, in the main,aphids, suchas the green peach aphid (Myzus persicae), the bean aphid(Doralis fabae);

scales,

such as Aspidiotus hederae, Lecanium hespedridum, Pseudococcusmaritimus, Thysanoptera, such as Hercinothrips femoralis; and bugs, suchas-the beet bug (Piesma quadrata) and the bed bug lectularius); and thelike.

With the biting insects contemplated herein there are classed, in themain, butterfly caterpillars, such as the Plutella maculipermis andLymantria dispar; beetles, such as granary weevils (Sitophilusgranarious), the Colorado beetle (Leptinolarsa decemlineata), and alsospecies living in the soil, such as wireworms (Agriotes sp.) and larvaeof the cockchafer (Melolontha melolontha); cockroaches, cockroach(Blatella germanica); Orthoptera, such as the house cricket (Gryllusdomesticus); termites, such as Reticulitermes; and Hymenoptera, such asants; and the like.

The Diptera contemplated herein comprise in particular the flies, suchas the vinegar fly (Drosophila melanogaster), the Mediterranean fruitfly (Ceratitis capitata), the house fly (Musca domestica), and gnats,such as the mosquitoes: Aedes aegypti, Culex pipiens and Anophelesstephensi; and blow flies such as Lucilia sericata and Chrysomyachloropyga; and the like.

In the case of the mites contemplated herein, particularly important arethe spider mites (Tetranychidae) such as the two-spotted spider mite(Tetranychus urticae), the European red mite (Paratetranychus pilosus);gall mites, such as the currant gall mite (Eriophyes ribis) andtarsonemids, such as Tarsorlemus palllkius; and ticks, such as therelapsing fever tick (Ornithodorus moubata) and Boophilus microplus; andthe like.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions with'conventional inert (i.e., plant compatible or herbicidally inert)pesticidal diluents or extenders, i.e., conventional pesticidaldispersible carrier vehicles such as solutions, emulsions, suspensions,emulsifiable concentrates, spray powders, pastes, soluble powders,dusting agents, granules, etc. These are prepared in known manner, forinstance by extending the active compounds with convential pesticidaldispersible liquid diluent carriers and/or dispersible solid carriersoptionally with the use of carrier vehicle assistants, e.g.,conventional pesticidal surface-active agents, including emulsifyingagents and/or dispersing agents, whereby, for example, in the case wherewater is used as diluent, organic sol-' vents may be added as auxiliarysolvents. The following may be chiefly considered for use asconventional carrier vehicles for this purpose: inert dispersible liquiddiluent carriers, including inert organic solvents, such as aromatichydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated,especially chlorinated, aromatic hydrocarbons (e.g., chlorobenzenes,etc.), paraffins' (e.g., petroleum fractions), chlorinated aliphatichydrocarbons (e.g., methylene chloride, etc.), alcohols (e.g., methanol,ethanol, propanol, butanol, etc.), amines (e.g., ethanolamine, etc.),ethers, ether-alcohols (e.g., glycol monomethyl ether, etc.), amides(e.g., dimethyl formamide, etc.), sulfoxides (e.g.,

dimethyl sulfoxide, etc.), ketones (e.g., acetone, etc.)

and/or water, as well as inert dispersible finely divided solidcarriers, such as ground natural minerals (e.g.,

such as the German kaolins, alumina, silica, chalk, i.e. calciumcarbonate, talc, kieselguhr, etc.) and ground synthetic minerals (e,g.,highly dispersed silicic acid, silicates, e.g., alkali silicates, etc.);whereas the following may be chiefly considered for use as conventionalcarrier vehicle assistants, e.g., surface-active agents, for thispurpose: emulsifying agents, such as non-ionic and/or anionicemulsifying agents (e.g., polyethylene oxide esters of fatty acids,polyethlene oxide ethers of fatty alcohols, alkyl sulfonates, arylsulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesiumstearate, sodium oleate, etc.); and/or dispersing agents, such aslignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other nematocides,acaricides, insecticides, fungicides, and the like, or herbicides,bactericides, etc., if desired, or in the form of particular dosagepreparations for specific application made therefrom, such as solutions,emulsions, suspensions, powders, pastes, and granules which are thusready for use.

As concerns commercially marketed preparations,

these generally contemplate carrier composition mix tures in which theactive compound is present in an amount substantially between about 0.1-95 percent by weight, and preferably 05-90 percent by weight, of themixture, whereas carrier composition mixtures suitable for directapplication or field application generally contemplate those in whichthe active compound is present in an amount substantially between about0.00001-20 percent, preferably 0.01-5 percent, by weight of the mixture.Thus, the present invention contemplates over-all compositions whichcomprise mixtures of a conventional dispersible carrier vehicle such as(l) a dispersible inert finely divided carrier solid, and/or (2) adispersible carrier liquid such as an inert organic solvent and/or waterpreferably including a surface-active effective amount of a carriervehicle assistant, e.g., a surface-active agent, such as an emulsifyingagent and/or a dispersing agent, and an amount of the active compoundwhich is effective for the purpose in question and which is generallybetween about 0.0000l-95 percent, and preferably 0.01-95 percent, byweight of the mixture.

The active compunds can also be used in accordance with the well knownultra-low-volume process with good success, i.e., by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment in finelydivided form, e.g,, average particle diameter of from 50-100 microns, oreven less, i.e., mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/acre, preferably 2-16 fluidounces/acre, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95 percent by weight ofactive compound or even the 100 percent active substance alone, e.g.,about 20-100 percent by weight of the active compound.

In particular, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. nematodes, arthropods,i.e., insects and acarids, and fungi, especially soil-fungi, and moreparticularly, methods of combating at least one of nematodes, insects,acarids, and fungi, which comprise applying to at least one ofcorrespondingly (a) such nematodes, (b) such insects, (c) such acarids,(d) such fungi, and (e) the corresponding habitat thereof, i.e., thelocus to be protected, a correspondingly combative or toxic amount,i.e., a nematocidally, arthropodicidally, especially insecticidally oracaricidally, and/or fungicidally, effective amount of the particularactive compound of the invention alone or together with a carriervehicle as noted above. The instant formulations or compositions areapplied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, sprinkling, pouring,fumigating, and the like.

It will be appreciated by the artisan that when using the instant activecompounds against nematodes, such active compounds are preferablyuniformly scattered in applied amounts of 5-50 kg of active compound perhectare and then worked into the soil.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention 'is illustrated, withoutlimitation, by the following examples:

EXAMPLE 1 Critical concentration test Test nematode: Meloizwgyneincognita Solvent: 3 parts by weight acetone Emulsifier: 1 part byweight alkylaryl polyglycol ether To produce a suitable preparation ofthe particular active compound, 1 part by weight of such active compoundis mixed with the stated amount of solvent, the stated amount ofemulsifier is added thereto, and the resulting concentrate is dilutedwith water to the desired final concentration.

The preparation of the given active compound is intimately mixed withsoil which is heavily infested with the test nematodes. Theconcentration of the active compound in the preparation is ofpractically no importance; only the amount of active compound per unitvoluume of soil, which is given in p.p.m., is decisive. The soil isfilled into pots, leettuce is sown in and the pots are kept at agreenhouse temperature of 27 C. After 4 weeks, the lettuce roots areexamined for infestation with nematodes, and the degree of effectivenessof the given active compound is determined as a percentage. The degreeof effectiveness is percent when infestation is completely avoided; itis 0 percent when the infestation is exactly the same as in the case ofthe control plants in untreated soil which has been infested in the samemanner;

The particular active compounds tested, the amounts applied and theresults obtained can be seen from the following Table l:

TABLE 1.CRI'IICAL CONCENTRATION TEST Degree of efiectivtness as apercentage in the case of applied amounts of 13.19.11].

Active compound 20 10 5 2. 5

C:H5O i Q- IL-O Comparative preparation known from US.

Patent 2,761,806

11 CH; 100 as 95 50 0 ar U P OCH. CHCH2 e? /PO CH3 OH-CHQ ai u /PO CzHCHCH2 ar II CH-CH2 EXAMPLE 2 (51) $1 CCH s Plutella test Solvent: 3parts by weight acetone ctHv'n Emulsifier: 1 part by weight alkylarylpolyglycol 0 CHOH2 ether To produce a suitable preparation of theparticular active compound, 1 part by weight of such active compound ismixed with the stated amount of solvent con- EXAMPLE 3 taining thestated amount of emulsifier and the result- 45 lrzfilzoegfrearggalte 1sdlluted with water to the desired final Dmsophila test Solvent: 3 arts bwei ht acetone Cabbate leaves (Brasszca oleracea) are sprayed withEmulsifierP 1 Wei ht alk l l l 1 co the preparation of the given activecompound until dew ether p y g y ary p0 yg y moist and are then infestedwith caterpillars of the diamond-back moth (Plutella maculipennis).

After the specified period of time, the degree of destruction isdetermined as a percentage: 100 percent means that all the caterpillarsare killed, whereas 0 percent means that none of the caterpillars arekilled.

The particular active compounds tested, their concentrations, theevaluation time and the results obtained can be seen from the followingTable 2:

TABLE 2 Plutella test Active Concentration Degree of compound of activedestruction in compound in after 3 days To produce a suitablepreparation of the particular active compound, 1 part by weight of suchactive compound is mixed with the stated amount of solvent containingthe stated amount of emulsifier, and the resulting concentrate isdiluted with water to the desired final concentration.

1 cc of the preparation of the given active compound is applied with apipette to a filter paper disc of 7 cm diameter. The wet disc is placedin a glass vessel containing 50 vinegar flies (Drosophila melanogaster)and covered with a glass plate.

After the specified period of time, the destruction is determined as apercentage: percent means that all the flies are killed; 0 percent meansthat none of the flies are killed.

The particular active compounds tested, their concentrations, theevaluation time and the degree of destruction can be seen from thefollowing Table 3:

TABLE 3.DRos01 1nLA TEST Degree 01 Concentration destruction of activein percent compound in after 24 Active compound percent hours /P-CII;ortc1 (CH2 \ll P()C2I'I5 CIT-CH2 l 1 -0- sc1r 1 GIL-C(z EXAMPLE 4EXAMPLE 5 Tetranychus test 01 C1 Solvent: 3 parts by weight acetone S 5s Emuls1fier: 1 part by weight alkylaryl polyglycol ether To produce asuitable preparation of the particular LHTCHZ active compound, 1 part byweight of such active compound is mixed with the stated amount ofsolvent containing the stated amount of emulsifier, and the resultingconcentrate is diluted with water to the desired final concentration.

Bean plants (Phaseous vulgaris), which have a height of approximately10-30 cm., are sprayed with the preparation of the given active compounduntil dripping wet. These bean plants are heavily infested with spidermites (Tetranychus urticae) in all stages of development.

After the specified period of time, the effectiveness of the activecompound preparation is determined by counting the dead mites. Thedegree of destruction thus obtained is expressed as a percentage: 100percent means that all the spider mites are killed, whereas 0 percentmeans that none of the spider mites are killed.

(III-CH:

The process for preparing the active compounds according to the presentinvention is illustrated, without limitation, by the following furtherExamples 62 g (0.33 mol) l-thiono-l,3-dichoro-phospholine (b.p. to 103C/3 mm Hg) are provided in ml benzene. To this mixture there are addeddropwise at 10 to 15 C, with vigorous stirring, 76 ml of a methanolicsolution of sodium methylate which contains 0.33 mol of sodiummethylate. The reaction mixture is stirred for a further 2 hours at 40C, and then poured into ice water. The mixture is taken up in ether, theethereal solution is dried over sodium sulfate, and the solvent is drawnoff. The residue is then distilled under reduced pressure; thecorresponding l-methoxyl-thiono-3-chloro-phospholine isomer mixtureboils at 96 to 98 C/2 mm Hg.

The yield is 50 g (83 percent of the theory) Analysis: Calculated for CH C 1 OPS (molecular weight 182.5):

P S Cl 16.99%; 17.53%; 1944%; Found: 17.18% 17.70% 19.11%,

The DL of the corresponding compound in the rat per os lies about 1,000mg/kg.

EXAMPLE 6 The mixture of isomers obtained according to Example 5 isseparated at room temperature by column chromatography with silica gel,a mixture of benzene and petroleum ether in a volume ratio of 1:1serving as flow medium. The purity of the corresponding compound therebyrecovered, i.e., l-methoxy-l-thiono-3-chloro- A -phospholine, and itsidentity with the formula stated EXAMPLE 7 The compound of the aboveformula, i.e., l-methoxy-l-thion-3-chloro-A -phospholine, is obtainedand identified according to the method stated in Example 6 from themixture prepared according to Example 5.

To a mixture of 62 g (0.33 mol) 1-thiono-l,3- dichlorophospholine and150 ml benzene there are added dropwise at to C, with vigorous stirring,145 ml of an ethanolic solution which contains 0.33 mol sodium ethylate.The reaction mixture is subsequentlystirred for a further 2 hours atroom temperature and then poured into ice water. Working up of themixture takes place as stated in Example 5.

The corresponding l-ethoxy- 1-thiono-3- chlorophospholine isomer mixture(A and A boils at 93 to 95 C/2 mm Hg (separation of the isomers ispossible, as described above in Examples 6 and 7).

The yield is 52 g (79 percent of the theory) Analysis: Calculated for CH C lOPS (molecular weight 196.5):

P 5 Cl 15.78%; 16.28%; 18.04%; Found: 15.72%; 16.27%; 17.96%.

EXAMPLE 9 (31 $1 C-CH S C=CH S 2 11 P or CH-Cfiz \O C Hn CHz-CHZ 0- .'17iw 1) (7'1) 50 ml isopropanol are added over a period of 10- minutes,at 40 C, to 62 g (0.33 mol) l-thiono-1,3- dichlorophospholine; 27 g(0.33 mol) pyridine are then added dropwise to the mixture, withstirring, and the resulting mixture is heated at 40 to 50 C for afurther 2 hours. Thereafter, the reaction mixture is poured into icewater, the product is extracted with carbon tetrachloride, and theextraction solution is dried over sodium sulfate. Finally, the solventis drawn ofi under reduced pressure and the residue is distilled. Thecorresponding l-isopropoxyl -thiono-3 chlorophospholine isomer mixture(A and A boils at 99 to 101 C/2 mm Hg.

The yield is 50 g (72 percent of the theory) Analysis: Calculated for Cl-l C 1 OPS (molecular weight 210.5):

P 5 14.71%; 15.20%; Found: 14.85%; 15.05%.

EXAMPLE 10 01 (I31 :CHz S (3:05 /S 1 011 0g; O-C Hg-11Ol 0112-011,o-clHr-n The above compounds are obtained in an analogous manner to thatof the preceding Example with a yield of percent of the theory. Thecorresponding l-n-butoxy-1-thiono-3-chloro-phospholine isomer mixture (Aand A) boils at 124 to 127 C under a pressure of 3 mm Hg.

EXAMPLE 1 l :1 11 CCH2 s 0::011 s Preparation is effected in a manneranalogous to the procedure of Example 9. The corresponding l-(B-chloroethoxy 1 -thiono-3-chloro-ph0spholine isomer mixture (A and A isobtained in 50 percent yield and boils at 133 C/3 mm Hg.

In an analogous manner to that described in Example 9, the correspondingl-allyloxyl-thiono-3ch1orophospholine isomer mixture (A and A isobtained in a yield of 81 percent of the theory. The correspondingproduct boils at 101to 103 C/2 mm Hg.

EXAMPLE 13 (3H3 (3H3 0*0112 s 0:011 s or .11 011z 00113 0111-0112 0-011.

50 ml of a solution which contains 0.25 mol sodium methylate dissolvedin methanol are added to a suspension of 49 g (0.25 mol)2,4,5-trichloro-phenol (m.p. 64 to 67 C) in 250 ml benzene. Methanol andbenzene are then distilled off with vigrous stirring and the residue istaken up in 250 ml methylethyl ketone. 47 g (0.25 mol) l-thiono-l ,3-dichlorophospholine are then added dropwise to the mixture at C, withstirring, and heating at 45 to 50 C is carried out for a further 3hours. The reaction mixture is then poured into cold water, the organicphase is diluted with ether and the ethereal layer is separated anddried over sodium sulfate. After the solvent has been distilled off, areddish-brown, water-insoluble, non-distillable oil is obtained. Theyield of the corresponding l-(2,4',5 '-trich10rophenyloxy l -thiono-3-chloro-phospholine isomer mixture (A and A is about 80 percent of thetheory.

EXAMPLE 15 Preparation is effected in the manner described in Example 15above, starting from 4-methylmercaptophenol and sodium methylatefollowed by reaction of the sodium salt formed withl-thiono-1,3-dichlorophospholine. The correspondingl-(4-methylmercapto-phenyloxy)- l-thiono-3-chlorophospholine isomermixture (A and A is a water-insoluble, non-distillable oil.

The yield is percent of the theory.

It will be realized by the skilled artisan that each of thecorresponding isomers in the foregoing production examples can beisolated from the isomer mixture in a suitable manner such as thatdescribed in Examples 6 and 7 above, and that each said isomer possessesthe corresponding physical properties noted in said production examplesas well as the corresponding pesticidal activity in question.

More specifically, it will be realized that all of the foregoingcompounds contemplated by the present invention possess the desiredselective pesticidal, especially nematocidal, arthropodicidal, i.e.,insecticidal or acaricidal, and fungicidal properties for combatingnematodes, insects and acarids, as well as fungi, and that suchcompounds have not only a very slight toxicity toward warm-bloodedcreatures, but also a concomitantly low phytotoxicity.

As may be used herein, the terms arthropod, arthropodicidal andarthropodicide contemplate specifically both insects and acarids. Thus,the insects and acarids may be considered herein collectively asarthropods to be combated in accordance with the invention, andaccordingly the insecticidal and/or acaricidal activity may be termedarthropodicidal activity, and the concomitant combative or effectiveamount used will be an arthropodicadally effective amount which ineffect means an insecticidally or acaricidally effective amount of theactive compound for the desired purposes.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and thatvariousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

l. A pesticidal composition wherein the pests are selected from thegroup consisting of insects, acarids, nematodes and fungi comprising apesticidally effective amount of a compound of the formula or mixturesthereof,

wherein R is selected from the group consisting of chloro and alkyl ofone to four carbon atoms, and R is selected from the group consisting ofalkyl of one to six carbon atoms, alkenyl of two to four carbon atoms,chloroalkyl of one to four carbon atoms, alkylphenyl having one to fourcarbon atoms in the alkyl moiety, alkylmercaptophenyl having one tofungus which c omprises applying to such pest or its habitat apestlcidal y effective amount of a compound of the formula H-GHz CHz-CH:

of mixtures thereof,

wherein R is selected from the group consisting of chloro and alkyl ofone to four carbon atoms, and R is selected from the group. consistingof alkyl of one to six carbon atoms, alkenyl of two to four carbonatoms, chloroalkyl of one to four carbon atoms, alkylphenyl having oneto four carbon atoms in the alkyl moiety, alkylmercaptophenyl having oneto four carbon atoms in the alkylmercapto moiety, and chloro-subsitutedphenyl.

4. The method according to claim 3 wherein R is selected from the groupconsisting of chloro and C, alkyl, and

R is selected from the group consisting of C, alkyl, C alkenyl, chloro-Calkyl, C alkylphenyl, C alkylmercaptophenyl, and mono to trichloro-phenyl.

5. The method according to claim 3 wherein R is selected from the groupconsisting of chloro, and C alkyl, and

R is selected from the group consisting of C alkyl, C alkylphenyl, and Calkylmercaptophenyl.

6. The method according to claim 3 wherein such compound is l-methoxy-1-thiono-3-methyl-A phospholine of the formula 7. The method accordingto claim 3 wherein such compound is l-methoxyl -thiono-3-chloro-Aphospholine of the formula PO-CH3 CHz-Cfiz 8. The method according toclaim 3 wherein such compound is l-methoxyl -thiono-3-chloro- Aphospholine of the formula Cl (\I-CH: S i GEL-C OCHa 9. The methodaccording to claim 3 wherein such compound isl-(4'-methylmercapto-phenoxy)-1- thiono-3-chloro-A -phospholine of theformula CHCH2 10. The method according to claim 3 wherein such compoundis l-(4'-tert.-butyl-phenoxy)-l-thiono-3- chloro-A -phospholine of theformula 11. The method according to claim 3 wherein such compound isl-(A-chloro-ethoxy)-l-thiono-3- chloro- A -phospholine of the formula112. The method according to claim 3 wherein such compound is 1-(2', 4',5'-trichloro-phenoxy)-l-thiono- 3-chloro-A -phospholine of the formula

2. A composition according to claim 1 wherein said compound is:1-methoxy-1-thiono-3-methyl- Delta 3 -phospholine,1-methoxy-1-thiono-3-chloro- Delta 2-phospholine,1-methoxy-1-thiono-3-chloro- Delta 3-phospholine,1-(4''-methylmercapto-phenoxy)-1-thiono-3-chloro- Delta 3-phospholine,1-(4''-tert.-butyl-phenoxy)-1-thiono-3-chloro- Delta 3-phospholine, 1-(Beta -chloro-ethoxy)-1-thiono-3-chloro- Delta 3-phospholine, or1-(2'',4'',5''-trichloro-phenoxy)-1-thiono-3-chloro- Delta3-phospholine.
 3. The method of combatting a pest selected from thegroup consisting of an insect, acarid, nematode and fungus whichcomprises applying to such pest or its habitat a pesticidally effectiveamount of a compound of the formula
 4. The method according to claim 3wherein R is selected from the group consisting of chloro and C1 4alkyl, and R'' is selected from the group consisting of C1 4 alkyl, C3alkenyl, chloro-C1 3 alkyl, C1 4 alkylphenyl, C1 4 alkylmercaptophenyl,and mono to tri chloro-phenyl.
 5. The method according to claim 3wherein R is selected from the group consisting of chloro, and C1 2alkyl, and R'' is selected from the group consisting of C1 4 alkyl, C1 4alkylphenyl, and C1 4 alkylmercaptophenyl.
 6. The method according toclaim 3 wherein such compound is 1-methoxy-1-thiono-3-methyl- Delta3-phospholIne of the formula
 7. The method according to claim 3 whereinsuch compound is 1-methoxy-1-thiono-3-chloro- Delta 2-phospholine of theformula
 8. The method according to claim 3 wherein such compound is1-methoxy-1-thiono-3-chloro- Delta 3phospholine of the formula
 9. Themethod according to claim 3 wherein such compound is1-(4''-methylmercapto-phenoxy)-1-thiono-3-chloro- Delta 3-phospholine ofthe formula
 10. The method according to claim 3 wherein such compound is1-(4''-tert.-butyl-phenoxy)-1-thiono-3- chloro- Delta 3-phospholine ofthe formula
 11. The method according to claim 3 wherein such compound is1-( Delta -chloro-ethoxy)-1-thiono-3- chloro- Delta 3-phospholine of theformula
 12. The method according to claim 3 wherein such compound is1-(2'', 4'', 5''-trichloro-phenoxy)-1-thiono-3-chloro- Delta3-phospholine of the formula